Plant protection composition absorbates and products for plant protection

ABSTRACT

Absorbates having a high loading of particular substances for use in plant protection compositions, the use of a special process for the preparation of the absorbates and products for plant protection comprising the absorbates.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to novel absorbates with a specialcomposition, in particular a high loading of particular substances foruse in plant protection compositions, the use of a special process forthe preparation of the absorbates and products for plant protectioncomprising the absorbates.

2. Description of the Related Art

In the field of products for plant protection, a distinction is madebetween solid and liquid formulation types. In the field of solidformulations, liquid or meltable active substances, together withauxiliaries (for example, surfactants and disintegrating agents), areattached to carrier materials. With solid active substances, the carriermaterials serve firstly as fillers. With liquid or low melting pointactive substances the carriers serve to absorb the liquid or low meltingpoint active substances. Superficially dry absorbates are obtainablewhich are easy to handle and which maybe marketed either directly aspowders (WP, wettable powder) or, processed, as granules/extrudates (WG,water dispersible granules).

In the case of WGs, a pre-prepared absorbate powder may be converted toa granule form or the product components maybe formed directly (forexample, by spray drying). A possible preparation of WGs by direct spraydrying of a dispersion of silica, active substance and additionalauxiliaries is disclosed, for example, in U.S. Pat. No. 6,869,914.

In particular with liquid or low melting point active substances andauxiliaries for plant protection compositions, subsequently referred toas “particular substances for use in plant protection compositions”, itis impossible with the processes known to date to prepare absorbateswith a desired high content of particular substances for use in plantprotection compositions. Thus, using conventional processes, absorbateswith satisfactory flowability can be prepared only up to 65% by weightbased on the total weight of the absorbate (based on a liquid density of1.00 g/ml).

In mechanical absorption processes, such as, for example, simple mixingof the components, a very broad distribution in the size of theagglomerates of the absorbates is to be expected in the region of thelimit load of the silica. This tends to greatly reduce the flowabilityof the resulting products and aggravates further handling (metering, andthe like). In addition, in conventional mixing processes it is difficultto avoid compacting agglomeration. Such compacting agglomerates areundesirable, for example when the product is used as WP, since they havea negative effect on the desired good disintegration behavior onredispersing in water.

Additional disadvantages of the absorbates of the state of the art are asometimes expensive preparation process and in particular a highproportion of expensive carrier materials, which also include carriermaterial silicas. In products for plant protection in particular, whichare produced and sold in very large amounts, even a small reduction inthe amounts of the carrier materials used would already be tremendouslyadvantageous economically and also ecologically.

SUMMARY OF THE INVENTION

It is accordingly an object of the present invention to provide novelabsorbates which do not exhibit at least some of the disadvantages ofthe absorbates of the state of the art or exhibit them only to a reducedextent and which make it possible to prepare novel products for plantprotection.

It is a further object of the invention to provide an absorbateincluding a carrier material and a plant protection material.

It is a further object of the invention to provide a process for makingabsorbates.

It is a further object of the invention to provide a process of applyingthe absorbates onto plants for plant protection.

This and other objects of the invention are achieved by the absorbatesand products for plant protection defined more fully in the claims, thedescription and the examples, and also the process for the preparationthereof more fully defined there.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows an embodiment of the invention including an autoclave; and

FIG. 2 shows an embodiment of the invention without an autoclave.

DETAILED DESCRIPTION OF THE INVENTION

It has been found, surprisingly, that it is possible, by the use of aspecial process for the absorption of liquids on carrier materials incombination with the selection of special carrier materials, to prepareabsorbates with a content of particular substances for use in plantprotection compositions of at least 70%, based on the total weight ofthe absorbates and on a liquid density of 1.00 g/ml. In addition to thehigh loading, it is also possible, by the use of special carriermaterials, to achieve a particularly good, i.e. complete or to thegreatest possible extent complete, desorption of the particularsubstances from the carried after redispersing the absorbates in water.

The absorbates according to the invention have the advantage that they,in comparison to absorbates of the state of the art, exhibit aconsiderably higher loading of absorbed particular substances for use inplant protection compositions and yet are superficially dry, resistantto compaction under pressure, and flow well.

Furthermore, an advantageously low cost for the absorbates can beachieved by the use of special carrier materials like precipitatedsilicas in combination with the high loading. In addition, therequirements and conditions of environmental protection may be metbecause the carrier materials are completely harmless ecologically.

A particular advantage of the use of precipitated silicas, pyrogenicsilicas and silica gels as carrier materials has proven to be that thephysicochemical properties thereof can be purposefully adapted to theparticular substance for use in plant protection compositions to beabsorbed or a mixture of substances comprising a particular substancefor use in plant protection compositions. In particular, the inventorshave found out that precipitation silicas, pyrogenic silicas and silicagels with a special pore distribution, when used in combination with thepreparation process according to the invention, provide absorbates thatexhibit both a high loading and excellent desorption properties.Precipitated silicas with a special pore distribution have proven to beparticularly advantageous in this regard.

An additional advantage of the absorbates according to the invention isthat they can also be prepared with particular substances for use inplant protection compositions which hitherto could only insufficientlybe brought into the form of absorbates. The reason is that no highdrying temperatures are necessary due to the use of a ConcentratedPowder Form (CPF) process.

Finally, the absorbates according to the invention exhibit anadvantageous agglomerate size distribution.

One embodiment of the invention includes absorbates, that comprise

-   -   at least one carrier material chosen from the group consisting        of precipitated silicas, pyrogenic silicas, silica gels, natural        clays, modified natural clays and diatomaceous earths, and    -   at least one particular substance for use in plant protection        compositions or a mixture of substances comprising at least one        particular substance for use in plant protection compositions,        and    -   that the proportion of the particular substance for use in plant        protection compositions or, in mixtures of at least two        particular substances for use in plant protection compositions,        the total amount of the particular substances for use in plant        protection compositions, X_(stand.), is 70% to 99%.

Another embodiment of the invention includes products for plantprotection comprising at least one absorbate according to the invention,and the use of an absorbate according to the invention for thepreparation of products for plant protection.

The invention further includes the use of at least one precipitatedsilica, pyrogenic silica, silica gel, natural clay, modified naturalclay and diatomaceous earth for the preparation of absorbates loadedwith particular substances for use in plant protection compositions ormixtures of at least two particular substances for use in plantprotection compositions, the total amount of the particular substancesfor use in plant protection compositions being from X_(stand.)=70% to99%.

The use of a process comprising at least the following stages is alsoincluded in the invention:

-   -   providing a liquid, comprising at least one liquid or molten        particular substance for use in plant protection compositions        and/or at least one liquid or molten mixture of substances        comprising at least one particular substance for use in plant        protection compositions, in a feed vessel,    -   mixing and/or partly dissolving a gas, preferably under elevated        pressure, particularly preferably in the supercritical        condition, in particular CO₂ at a pressure p>73.83 bar and at a        temperature T>31.04° C., in the liquid, preferably in a mixer        and/or pressurized vessel,    -   feeding the liquid/gas solution/melt to an expansion element,    -   conveying the liquid/gas solution or the liquid/gas melt through        an expansion element to expand the liquid/gas solution or the        liquid/gas melt,    -   adding at least one solid pulverulent carrier material to the        expanded liquid/gas solution or liquid/gas melt.

Another embodiment of the invention includes a process comprising theuse of the abovementioned process for the preparation of absorbatescharged with particular substances for use in plant protectioncompositions and the subsequent further processing of these absorbatesto give products for plant protection.

The term “particular substances for use in plant protectioncompositions” is understood to mean, within the meaning of the presentinvention, liquid or low melting point (e.g., melting point<=80° C.)active substances and/or auxiliaries for plant protection compositions.

Active substances for plant protection compositions are substances whichhave a direct or indirect biological activity against attack by pests onor diseases of plants or which affect the metabolism or the growth ofthe plants. These include the active substances which are suitable forpreventing, controlling or combating attack by pests and/or forpreventing, regulating and/or minimizing damage to or diseases ofplants, wood or wood products which can occur during the growth,production, processing, storage, transportation or marketing and/or forregulating, minimizing or preventing the effects of insects, acarids orother pests on working animals which are fed with the plants. Thisincludes active substances which are certainly for use as insect orplant growth regulators and also defoliants, desiccants, agents forregulating, weakening or preventing the premature putrefaction of fruitand substances for application to cereals, either before or afterharvesting, in order to protect the harvested crop from damage duringstorage and transportation. Further details on the definition,nomenclature and characterization of active substances for plantprotection compositions can be taken from the manual “PesticideSpecifications,” Manual on Development and Use of FAO and WHOSpecifications for Pesticides, published by the World HealthOrganization (WHO) and Food and Agriculture Organization of the UnitedStates, Rome, 2002, ISBN 92-5-104857-6. The entire contents of thispublication are hereby incorporated by reference herein.

The active substances for plant protection compositions are preferablyliquid or low melting point active substances, such as can be taken, forexample, from the CIPAC manual H, “Analysis of Technical and FormulatedPesticides”, published by the Collaborative International PesticidesAnalytical Council Limited, 1998, ISBN 0902951130. The contents of thisdocument are hereby explicitly incorporated by reference herein.

The term “auxiliaries for plant protection compositions” is understoodas meaning, within the meaning of the present invention, substanceswhich are used to emulsify or disperse the active substance or whichmake possible the problem-free application of the formulation. Examplesof auxiliaries for plant protection compositions can be taken from EP 1319 336 A1. These auxiliaries are preferably liquid auxiliaries,low-melting-point auxiliaries or auxiliaries soluble in the activesubstance. The following are particularly preferred as auxiliaries:

-   -   surfactants according to EP 1 319 336 A1, paragraphs 0030 and        0038 to 0041    -   buffers according to EP 1 319 336 A1, paragraph 0048    -   antifoaming agents according to EP 1 319 336 A1, paragraph 0043

The entire contents of EP 1 319 336 A1 and in particular the paragraphsexplicitly mentioned above are incorporated herein by reference.

The content of particular substance for use in plant protectioncompositions is determined in the following way. Porous structuresabsorb always with reference to volume. Consequently, the use of liquidsof higher density generally results in higher loadings by weight incomparison to liquids of low density. In order to be able to givecomparable details, the proportion of particular substance for use inplant protection compositions is accordingly given, in the context ofthe present invention, as concentration by weight, based on a liquiddensity of 1.00 g/ml and the total weight of the absorbate.

The standardization with regard to a liquid density of 1.00 g/ml iscarried out according to formula (I):

$\begin{matrix}{X_{{stand}.} = \frac{100}{{\rho_{l}^{*}\left( {\frac{100}{X_{before}} - 1} \right)} + 1}} & {{formula}\mspace{14mu}(I)}\end{matrix}$

with

-   -   X_(stand.)=concentration by weight standardized with regard to a        liquid density of 1.00 g/ml, given in %,    -   X_(before)=concentration by weight before standardization, in %,    -   ρ_(l)=density of the absorbed particular substance for use in        plant protection compositions or of the mixture of particular        substances for use in plant protection compositions, in g/ml.

The loading by weight before the standardization is calculated accordingto formula (II) as follows:

$\begin{matrix}{X_{before} = {\frac{W_{1\;{{abs}.}}}{W_{{abs}.{total}}}*100\%}} & {{formula}\mspace{14mu}({II})}\end{matrix}$

with

-   -   W_(labs.)=weight of the absorbed particular substance for use in        plant protection compositions, in g,    -   W_(abs. total)=total weight of the absorbate, in g.

As already mentioned above, the standardization is necessary since,without considering the density of the absorbed liquid, no statement canbe made with regard to how heavily loaded the carrier material reallyis. Thus, the carrier in an absorbate in which 50 g of carrier materialhas absorbed 50 g of a liquid with a density of 1.00 g/ml is much moreheavily loaded (it has to absorb more liquid volume) than a carrier inan absorbate in which 50 g of carrier material has absorbed 50 g of aliquid with a density of 1.30 g/ml. X_(stand.) accordingly describes theconcentration by weight of an absorbate of a liquid with a density 1g/cm³ which comprise the same volume of liquid as the actual absorbate.The consequence of this is that, for a liquid density of ρl=1, thestandardized loading by weight X_(stand.) is the same as the loading byweight before the standardization X_(before). However, if a liquid witha density of 1.30 g/ml is absorbed, the standardized loading by weightX_(stand.) is thus smaller than the loading by weight before thestandardization X_(before). In this case, the circumstance isaccordingly taken into account that the carrier, because of the liquiddensity of 1.30 g/ml, has to absorb a smaller volume of liquid andaccordingly a higher loading potential is by and large available withthis liquid.

The following calculation examples should show this more clearly:

Calculation Example 1

A 70% absorbate of a particular liquid for use in plant protectioncompositions with a density of 1.23 g/ml corresponds, afterstandardization with regard to a liquid density of 1.00 g/ml, to anabsorbate with a loading by weight ofX _(stand.)=100/(1.23*((100/70)−1)+1)=65.48%.

Calculation Example 2

116.7 g of a liquid with a density of 1.30 g/ml are absorbed on 50 g ofsilica. This givesX _(before)=116.7/(116.7+50)*100=70%

This in turn corresponds to a standardized loading of:X _(stand.)=100/(1.30*((100/70)−1)+1)=64.22%.

The absorbates according to the invention, loaded with particularsubstances for use in plant protection compositions, are distinguishedin that

-   -   at least one carrier material chosen from the group consisting        of precipitated silicas, pyrogenic silicas, silica gels, natural        clays, modified natural clays and diatomaceous earths is        present,    -   at least one particular substance for use in plant protection        compositions or a mixture of substances comprising at least one        particular substance for use in plant protection compositions is        present as active substance, and    -   the proportion of particular substances for use in plant        protection compositions or, in mixtures of at least two        particular substances for use in plant protection compositions,        the total amount of particular substances for use in plant        protection compositions is from X_(stand.)=70% by weight to 99%        by weight.

The carrier material preferably exhibits a tapped density of less than200 g/l, very particularly preferably <150 g/l and in particular <100g/l. The adsorbates according to the invention particularly preferablycomprise at least one precipitated silica, pyrogenic silica or silicagel as carrier material.

In a preferred embodiment of the present invention, the carrier materialexhibits a

-   -   proportion of the micropore volume, based on the total pore        volume, of less than or equal to 10% by volume, preferably less        than or equal to 7% by volume, particularly preferably less than        or equal to 5% by volume and in particular 0.01 to 5% by volume,    -   and/or a DBP (di-butyl-phthalate) absorption of greater than or        equal to 150 g/100 g, preferably between 200 and 450 g/100 g.

In a preferred version of this embodiment, the carrier material is aprecipitated silica, a pyrogenic silica or a silica gel and particularlypreferably a precipitated silica.

The surface of the carrier materials, in particular of silicas andsilica gels, can be treated with a surface-modifying agent. Hydrophobicor partially hydrophobic carriers, e.g., may consequently be concerned.

Contrary to the teaching of the state of the art, such as, for example,WO 99/17868, the inventors of the present invention have recognized thatit is important, for the preparation of absorbates with a high contentof suitable substances for use in plant protection compositions whichsimultaneously exhibit good desorption properties, for the carriermaterials used to exhibit a particular pore volume distribution, i.e. alow proportion of micropore volume. Otherwise, it may happen that thecarrier materials indeed absorb a high amount of active substance butthat this active substance is only re-released very incompletely or veryslowly.

The amount X_(stand.) of particular substances for use in plantprotection compositions or, in mixtures of at least two particularsubstances for use in plant protection compositions, the total amount ofparticular substances for use in plant protection compositions ispreferably between 70 and 95%, particularly preferably between 75 and95% and in particular between 81 and 90%.

It is preferable for the absorbates according to the invention tocomprise only the carrier material and the particular substance(s) foruse in plant protection compositions.

The absorbates according to the invention preferably exist in the formof

-   -   solid formulations for direct use, such as dustable powders        (DP), powders for dry seed treatment (DS), granules (GR) or        tablets for direct application (DT),    -   solid formulations for dispersion, such as wettable powders        (WP), water dispersible powders for seed treatment (WS), water        dispersible granules (WG), water dispersible tablets (WT),        emulsifiable granules (EG) or emulsifiable powders (EP),    -   solid formulations for dissolution before application, such as        water soluble powders (SP), water soluble powders for seed        treatment (SS), water soluble granules (SG) or water soluble        tablets (ST).

WG or WP formulations are particularly preferred.

The abovementioned formulation forms and in particular the abbreviationsused correspond to the internationally recognized usage. Details can befound in the manual “Pesticide Specifications,” Manual on Developmentand Use of FAO and WHO Specifications for Pesticides, published by theWorld Health Organization (WHO) and the Food and AgricultureOrganization of the United States, Rome, 2002, ISBN 92-5-104857-6,Appendix E. The entire contents of this publication and in particular ofAppendix E are incorporated herein by reference.

A process can be used for the preparation of the absorbates according tothe invention which comprises at least the following stages:

-   -   providing a liquid, comprising at least one liquid or molten        particular substance for use in plant protection compositions        and/or at least one liquid or molten mixture of substances        comprising at least one particular substance for use in plant        protection compositions, in a feed vessel,    -   mixing and/or partly dissolving a gas, preferably under elevated        pressure, particularly preferably in the supercritical        condition, in particular CO₂ at a pressure p>73.83 bar and at a        temperature T>31.04° C., in the liquid, preferably in a mixer        and/or pressurized vessel,    -   feeding the liquid/gas solution/melt to an expansion element,    -   conveying the liquid/gas solution or the liquid/gas melt through        an expansion element to expand the liquid/gas solution or the        liquid/gas melt,    -   adding at least one solid pulverulent carrier material to the        expanded liquid/gas solution or liquid/gas melt.

The substances defined earlier in the description of the absorbatesaccording to the invention can be used as carriers or as particularsubstance or substances for use in plant protection compositions.

Different gases can be used in the process which can be used accordingto the invention.

In principle, use may be made, as gas, of any gas which issatisfactorily dissolved in the liquid, to be sprayed, comprising atleast one liquid or molten particular substance for use in plantprotection compositions and/or at least one liquid or molten mixture ofsubstances comprising at least one particular substance for use in plantprotection compositions. Use may be made, as gas, for example, of carbondioxide, a hydrocarbon, in particular methane, ethane, propane, butane,ethene, propene or a halogenated hydrocarbon, an ether, an inert gas, inparticular nitrogen, helium or argon, a gaseous oxide, in particulardinitrogen oxide or sulphur dioxide, and ammonia. A mixture of two ormore of the abovementioned gases can also be used.

The dissolution of the gas or the mixing of the gas with the liquidcomprising at least one liquid or molten particular substance for use inplant protection compositions and/or at least one liquid or moltenmixture of substances comprising at least one particular substance foruse in plant protection compositions can be carried out in differentways. Thus, it is possible to carry out the dissolution or the mixing ina pressure-resistant, optionally heatable, feed vessel, e.g. a suitableautoclave. However, it is also possible to carry out the mixing ordissolution in an optionally heatable mixing assembly, in particular astatic mixer, which is connected downstream to an optionally heatable,pressure-resistant, feed vessel.

In a preferred embodiment, the use of a pressure-resistant, optionallyheatable, feed vessel is avoided. Instead, the liquid comprising atleast one liquid or molten particular substance for use in plantprotection compositions and/or at least one liquid or molten mixture ofsubstances comprising at least one particular substance for use in plantprotection compositions is placed in an optionally heatable feed vesselof any dimensions and fed by means of a suitable pump to a suitablemixing assembly, e.g. a static mixer, where the liquid is mixed with agas or the gas is dissolved in the liquid. The liquid/gas mixture or theliquid/gas solution/melt can subsequently be fed directly to anexpansion element.

Combinations of the processes described above are likewise possible.

The mixing or dissolution of the gas in the liquid is preferably carriedout at elevated pressure.

The elevated pressure under which the gas is dissolved in the liquidsubstance or mixture of substances can lie in the range from 5 bar to800 bar, is, however, preferably 10 bar to 350 bar and particularlypreferably lies in the range from 20 bar to 250 bar.

Preferably, the dissolution of the gas in the liquid substance ormixture of substances is accelerated by mixing the gas with the liquidsubstance or mixture of substances. This mixing can be carried out, forexample, by shaking or rolling a vessel in which the gas and the liquidare brought together. For example, this can be a pressurized vessel intowhich the liquid to be atomized is introduced. Alternatively, theliquid/melt can be stirred with a gas during and/or after the operationin which they are brought together. Yet another possible way ofachieving good intermixing of the gas with the liquid/melt to beatomized consists in pumping over the liquid/melt and/or the gas phasein different vessels or in recirculating the liquid/melt and/or the gasphase, i.e. pumping out from the pressurized vessel and refeeding thepressurized vessel in the region of the other phase each time. Aparticularly preferred possibility is the use of a static mixer, theliquid/melt and the gas phase very particularly preferably being broughttogether only directly in the mixer and/or at the inlet of the mixer.The abovementioned embodiments can also be combined.

It may be necessary for different parts of the plant to have to be ableto be heated externally in order to bring the particular substance foruse in plant protection compositions to the liquid form or to keep inthis form. It may be necessary for this to provide, e.g. feed vessels,supply lines, mixers, expansion element and valves, with suitableheating capabilities. Thus, for example, it may be necessary for thesupply lines between the feed vessel and the mixer and/or between themixer and the expansion element and/or the feed vessel and the expansionelement, and/or the feed vessel itself and/or the mixer and/or theexpansion element to have to be heated in order to keep in the liquidcondition the liquid comprising at least one liquid or molten particularsubstance for use in plant protection compositions and/or at least oneliquid or molten mixture of substances comprising at least oneparticular substance for use in plant protection compositions or themixture of the said liquid and the gas. In this connection, theoperation is preferably carried out with temperatures of up to 80° C.

Use may be made in the process according to the invention, as expansionelement, of any device which makes possible a satisfactorily fastexpansion of the liquid/gas solution. Use is preferably made, asexpansion element, of a nozzle, a diffuser, a capillary, an orifice, avalve or a combination of the abovementioned expansion elements.

In the expansion of the liquid/gas solution/melt, the temperature canfall below the solidification point of the substance or mixture ofsubstances. However, this is not absolutely necessary in order to obtainthe desired pulverulent product. In a number of application cases, ithas certainly proved to be convenient, on expanding the liquid/gassolution, to achieve a temperature which is at least in the vicinity ofthe solidification point of the substance or mixture of substances.

It is important, in the process according to the invention, for thesolid pulverulent carrier material added to be mixed with the liquid/gassolution/melt or, according to where the pulverulent auxiliary is fedin, with the liquid to be atomized comprising at least one liquid ormolten particular substance for use in plant protection compositionsand/or at least one liquid or molten mixture of substances comprising atleast one particular substance for use in plant protection compositions.

Various possibilities are available for achieving good intermixing ofthe carrier material with the liquid/gas solution/melt or the liquid tobe atomized comprising at least one liquid or molten particularsubstance for use in plant protection compositions and/or at least oneliquid or molten mixture of substances comprising at least oneparticular substance for use in plant protection compositions. Thus, thepulverulent carrier material can, for example, be metered in at thepoint where the liquid/gas solution/melt emerges from the expansionelement, thus at or shortly before the expansion point. The carriermaterial is then entrained in the free jet formed after the expansionpoint, the considerable and fast expansion in volume of the gas presentin the liquid/gas solution/melt ensuring extremely intensive vortexingand mixing of the carrier with the liquid to be atomized comprising atleast one liquid or molten particular substance for use in plantprotection compositions and/or at least one liquid or molten mixture ofsubstances comprising at least one particular substance for use in plantprotection compositions.

According to another embodiment of the process according to theinvention, the carrier is fed in in such a way that it surrounds inannular fashion, in the region of the outlet, the stream of substanceemerging from the expansion element. This can, e.g., be carried out witha ring nozzle, so that the free jet emerging from the expansion elementis at least partially encased by the carrier material. The encasing ofthe free jet with the carrier furthermore ensures that, just afteremergence from the expansion element, droplets of liquid possibly stillpresent cannot be deposited on a surrounding wall but are entrained.

It may be sensible to feed the stream of substance emerging from theexpansion element and the carrier to a diffuser in order to be able tocontrol the enlargement in cross section of the free jet. Furthermore,one or more flow separation edges can additionally, with the vortexingsproduced there, bring about even more intensive intermixing between thefree jet and the carrier.

In a preferred embodiment of the process according to the invention, theexpansion of the liquid/gas solution/melt is carried out in a spraytower. The carrier to be added can then, for example, be transported tothe spray tower by means of methods known to a person skilled in theart, e.g. by means of a screw conveyor or pneumatic conveyance, andmetered in at the desired point.

In preferred embodiments of the process according to the invention,additional gas, which can be described as “excess gas”, is addedadditionally to the gas which is already dissolved in the liquidcomprising at least one liquid or molten particular substance for use inplant protection compositions and/or at least one liquid or moltenmixture of substances comprising at least one particular substance foruse in plant protection compositions. This can be carried outparticularly advantageously in the region of the expansion element. Withthis excess gas, the temperature reached in the expansion operation canbe adjusted more independently. It is necessary neither for theliquid/gas solution/melt to be essentially saturated with the gas nor,for example, for a relatively high pressure to be chosen in order toachieve a gas concentration in the liquid sufficiently great for thedesired cooling down. Rather, it is possible to bring about the desiredcooling down in the region of the expansion point to a large extent bythe rapid expansion of the excess gas additionally supplied. Inaddition, the possibility arises of choosing, as excess gas, a gas whichis different from the gas dissolved in the liquid. For example, theexcess gas can be chosen with regard to the biggest possible lowering intemperature, while the gas to be dissolved in the liquid is decided uponaccording to other standpoints. In addition to better cooling down inthe region of the expansion point, the excess gas also results in aneven better intermixing or vortexing after the emergence of the streamof substance from the expansion element and accordingly in even smallerpowder particles.

Various possibilities exist with regard to the introduction of theexcess gas. According to one embodiment of the process according to theinvention, the excess gas is charged to the liquid/gas solution/meltbetween the pressurized vessel and the expansion element, in particularjust before the expansion point. In this connection, a static mixer, forexample, can be inserted for better mixing with the liquid/gassolution/melt.

According to another embodiment, the liquid/gas solution/melt andadditionally introduced excess gas are expanded together with oneanother in the expansion element by means of a twin-substance nozzle. Inthis embodiment, the excess gas is thus not added to the liquid/gassolution/melt but is fed directly to the expansion point, so that theliquid/gas solution/melt and the pure excess gas are expandedsimultaneously. The twin-substance nozzle can, for example, be such thatthe liquid/gas solution/melt emerges through a central channel, whilethe excess gas emerges through a ring channel which surrounds thecentral channel coaxially.

According to yet another embodiment, the excess gas is fed together withthe solid pulverulent auxiliary to the solution or to the substance ormixture of substances.

The process according to the invention can be operated both continuouslyand batchwise. For continuous operation, it may be necessary to providethe receiver, e.g. spray tower, for the absorbates according to theinvention with a suitable device for continuous feeding of theabsorbates according to the invention. Suitable techniques for this,e.g. screw conveyors or star feeders, are known to a person skilled inthe art.

As already intimated earlier, several effective embodiments of theprocess according to the invention are possible. FIG. 1 shows a possibleembodiment in which an autoclave is used for mixing or dissolving thegas with/in the liquid comprising at least one liquid or moltenparticular substance for use in plant protection compositions and/or atleast one liquid or molten mixture of substances comprising at least oneparticular substance for use in plant protection compositions.

FIG. 1 shows, as pressurized vessel, an autoclave 1 which is chargedwith the liquid to be atomized comprising at least one liquid or moltenparticular substance for use in plant protection compositions and/or atleast one liquid or molten mixture of substances comprising at least oneparticular substance for use in plant protection compositions.Subsequently, through suitable measures, for example by moving theautoclave 1 or the autoclave contents (e.g., by stirring or recycling),a chosen gas is dissolved under pressure in the liquid introduced. Thegas chosen is fed in in a conventional way and is not represented in thefigure. To accelerate the dissolution of gas in the liquid to beatomized, the liquid and the gas to be dissolved therein can optionallybe conveyed cocurrently through a static mixer 2 and can subsequently beintroduced into the autoclave 1. Depending on the type of gas chosen anddepending on the pressure chosen and the temperature, gas concentrationsbetween 1 and 90% by weight, preferably 5 to 50% by weight and inparticular 10 to 40% by weight can be achieved in the liquid phase. Thetemperature is expediently in the region of room or ambient temperature.However, with high viscous substances or mixtures of substances, ahigher temperature may even be required. It is essential for the liquidto be atomized comprising at least one liquid or molten particularsubstance for use in plant protection compositions and/or at least oneliquid or molten mixture of substances comprising at least oneparticular substance for use in plant protection compositions to bepresent in the pressurized vessel as liquid or suspension or melt.

The liquid/gas solution present in autoclave 1 after the dissolution ofthe gas is fed to a three-way valve 4 via a line 3. Additional gas,“excess gas”, is fed to the three-way valve 4 from a gas container 5 viaa line 6. The excess gas can be a different gas from that dissolved inthe liquid.

The liquid/gas solution and the excess gas introduced are led from thethree-way valve 4 to an expansion element, which here is a high pressurenozzle 7. An additional static mixer 8 can be inserted between the highpressure nozzle 7 and the three-way valve 4 in order to improve theincorporation of the excess gas in the liquid/gas solution. However, itis also possible to convey the contents of the autoclave 1 and theexcess gas, via the line 9, directly in each case to the static mixer 8and only there to intermix. The high pressure nozzle 7 is arranged atthe narrowest point of a diffuser 10, which is mounted in the lid of aspray tower 11. A solid pulverulent carrier material 13 is fed incontinuously via a feed hopper 12, as long as the liquid/gassolution/melt and the excess gas are flowing out of the high pressurenozzle 7. An annular passage, which first narrows and then again widensand through which the auxiliary 13 introduced flows, is formed betweenthe high pressure nozzle 7 and the inner wall of the feed hopper 12 orof the diffuser 10. The auxiliary thus surrounds in annular fashion thestream of substance flowing out of the high pressure nozzle 7. Theconveying of the auxiliary 13 into the feed hopper 12 can be carried outusing known methods, for example using pneumatic conveyance, throughvibrating bars, using a screw feeder or a star feeder, or the like.

The large increase in volume of the gas present in the liquid/gassolution/melt and also of the excess gas additionally introduced afteremergence from the high pressure nozzle 7 results in great turbulenceand accordingly in good intermixing of the auxiliary with the stream ofsubstance emerging from the high pressure nozzle 7. In the exemplaryembodiment shown, a flow separation edge 14 present in the diffuserfurther increases the turbulence.

The large reduction in temperature which accompanies the expansion ofthe gas dissolved in the liquid and also of the excess gas ensures,together with the high turbulence mentioned, such a rapid and intensiveintermixing with the auxiliary that the desired pulverulent finalproduct is already obtained with a spray tower height of only 1 m. Thepowder accumulates in the lower part of the spray tower 11 and can bewithdrawn conventionally at the outlet 15, optionally continuously orbatchwise.

The gas dissolved in the liquid and also the excess gas separate, afteremergence from the high pressure nozzle 7, from the substance or mixtureof substances to be atomized. In the exemplary embodiment shown, the gasthus released is drawn off in the upper region of the spray tower 11through a line 16. Discharge of fine particles through the line 16 isprevented by the settling zone present between the diffuser 10 and theinner wall of the spray tower. A fine part of atomized productnevertheless possibly present in the gas drawn off can be removed fromthe gas stream in a conventional fashion, e.g. using a cyclone 17,before an extraction fan indicated with 18.

Details of the process described above can be found in WO 99/17868. Theentire contents of WO 99/17868 are hereby explicitly incorporated byreference herein.

An additional, particularly preferred, embodiment of the processaccording to the invention is represented in FIG. 2.

The process according to FIG. 2 differs from the process according toFIG. 1 in that the use of an autoclave is avoided. Instead, the liquidcomprising at least one liquid or molten particular substance for use inplant protection compositions and/or at least one liquid or moltenmixture of substances comprising at least one particular substance foruse in plant protection compositions is fed from the vessel 18 and thegas is fed from the vessel 19 via the lines 20 and 21 directly to asuitable, e.g. static, mixer 22 and there intensively mixed with oneanother. The liquid/gas mixture is then directly fed from the mixer 22to the expansion element 23. This embodiment is spared the use of anexpensive high pressure vessel (autoclave) and can moreover result in areduction in the amount of the gas used. Furthermore, the process isoptimized by replacing a time consuming equilibration in the autoclave,as necessary in the process according to FIG. 1, by a faster intermixingin the mixer 22.

The liquid comprising at least one liquid or molten particular substancefor use in plant protection compositions and/or at least one liquid ormolten mixture of substances comprising at least one particularsubstance for use in plant protection compositions can, in the processaccording to FIG. 2, be introduced into a simple, optionally heatable,feed vessel of any size (vessel 18). This vessel 18 does not have to bepressure resistant. The liquid from the feed vessel 18 can be fed to themixer 22 by means of a suitable pump 24, e.g. a diaphragm metering pump,or pneumatically, there mixed with the gas and, subsequently, fed to theexpansion element 23. The expansion element 23 and the feeding of thecarrier material are generally employed as described in FIG. 1. In theembodiment according to FIG. 2, the spray tower can be provided with thecapability of discharging 15 the absorbates according to the inventioncontinuously or batchwise. The absorbates can be discharged bytechniques known per se, such as, e.g., screw conveyors. Thisconfiguration of the equipment allows continuous process control. Forthis, it may be necessary for the carrier material likewise to be fedcontinuously. This can be carried out, e.g., by transporting the carriermaterial from an additional feed vessel 25, by air or gas supply or bymeans of a screw conveyor, directly to the desired point of entry on thespray tower. Detailed instructions with regard to the suitable point ofentry of the carrier material have already been given earlier. Thedischarging of the process gas can be carried out as described in FIG.1.

The present invention also includes products for plant protectioncomprising at least one absorbate according to the invention loaded withparticular substances for use in plant protection compositions. The term“products for plant protection” is to be understood as meaningcompositions which, in addition to at least one absorbate according tothe invention, also comprise at least one additional component which isnot bound to the carrier of the absorbate according to the invention.These include products which are suitable for preventing, controlling orcombating attack by pests and/or for preventing, regulating and/orminimizing damage to or diseases of plants, wood or wood products whichcan occur during the growth, production, processing, storage,transportation or marketing and/or for regulating, minimizing orpreventing the effects of insects, acarids or other pests on workinganimals which are fed with the plants. This includes compositions whichare certainly for use as insect or plant growth regulators and alsodefoliants, desiccants, agents for regulating, weakening or preventingthe premature putrefaction of fruit and substances for application tocereals, either before or after harvesting, in order to protect theharvested crop from damage during storage and transportation. Furtherdetails on the definition, nomenclature and characterization of productsfor plant protection can be taken from the manual “PesticideSpecifications”, Manual on Development and Use of FAO and WHOSpecifications for Pesticides, published by the World HealthOrganization (WHO) and Food and Agriculture Organization of the UnitedStates, Rome, 2002, ISBN 92-5-104857-6. The entire contents of thispublication are hereby explicitly incorporated by reference herein.

The products for plant protection according to the invention can existin the solid, liquid, oil or resin form or in the form of dispersions.They are preferably

-   -   solid formulations for direct use, such as dustable powders        (DP), powders for dry seed treatment (DS), granules (GR) or        tablets for direct application (DT),    -   solid formulations for dispersion, such as wettable powders        (WP), water dispersible powders for seed treatment (WS), water        dispersible granules (WG), water dispersible tablets (WT),        emulsifiable granules (EG) or emulsifiable powders (EP),    -   solid formulations for dissolution before application, such as        water soluble powders (SP), water soluble powders for seed        treatment (SS), water soluble granules (SG) or water soluble        tablets (ST)

or

-   -   liquid formulations, such as “aqueous suspension concentrates”        (SC), “suspension concentrates for seed treatment” (FS),        “oil-based suspension concentrates” (OD) or “aqueous        suspoemulsions” (SE).

The abovementioned formulation forms and in particular the abbreviationsused correspond to the internationally recognized usage. Details can befound in the manual “Pesticide Specifications”, Manual on Developmentand Use of FAO and WHO Specifications for Pesticides, published by theWorld Health Organization (WHO) and the Food and AgricultureOrganization of the United States, Rome, 2002, ISBN 92-5-104857-6,Appendix E. The entire contents of this publication and in particular ofAppendix E are incorporated herein by reference.

WP and WG formulations are particularly preferred.

The products for plant protection according to the invention can, inaddition to the absorbates according to the invention loaded withparticular substances for use in plant protection compositions, compriseadditional solid fillers, such as, e.g., natural calcium carbonate,clays or natural products, or additional auxiliaries, such as, e.g.biocides, thickeners, antifreeze agents or binders.

The products for plant protection according to the invention can beprepared by bringing at least one absorbate according to the invention,loaded with particular substances for use in plant protectioncompositions, into contact with at least one additional constituent ofthe products for plant protection. This can be carried out according tomixing processes known per se, such as, e.g., in tumbler mixers or panmixers.

Measurement Methods

Determination of the Pore Volume Distribution

The term “micropore volume” is understood to mean, within the context ofthe present invention, the volume of the pores with a pore diameter from0.4 nm to 2 nm. The micropore volume is determined by nitrogenadsorption according to DIN 66135 with the ASAP 2400 device,Micromeritics, according to the t-method. The evaluation is carried outvolumetrically using the t curve according to Harkins-Jura. The testspecimen has to be pretreated for the determination of the microporevolume. For this, the test specimen is predried at 105° C. for 24 h andsubsequently outgassed under vacuum at 200° C. for a time of 1 h.

The term “meso and macropore volume” is understood to mean, within thecontext of the present invention, the pore volume which is formed frompores with a diameter between 3.6 nm and 100 nm. This volume isdetermined using mercury porosimetry according to DIN 66133 with theAutopore-IV 9500 mercury porosimeter from Micromeritics. For thecalculation, the contact angle of the mercury is assumed to be 140° andthe surface tension thereof is assumed to be 480 mN/m. The pretreatmentof the test specimen is carried out analogously to that in thedetermination of the micropore volume.

The total pore volume is composed of the sum of the results of themicropore volume, determined by means of nitrogen adsorption, and of themeso/macropore volume, determined by means of mercury porosimetry,described above.

The calculation of the proportion of micropore volume (unit=[%]) iscarried out as follows:

${{Proportion}\mspace{14mu}{of}\mspace{14mu}{micropore}\mspace{14mu}{volume}} = {\frac{{micropore}\mspace{14mu}{volume}}{{{micropore}\mspace{14mu}{volume}} + {{{meso}/{macropore}}\mspace{14mu}{volume}}} \times 100}$

Determination of the DBP Absorption

The DBP absorption (DBP number), which is a measure of the absorbency ofthe precipitated silica, was determined according to the standard DIN53601 as follows:

12.50 g of pulverulent or spherical silica with a moisture content of0-10% (the moisture content is optionally adjusted by drying at 105° C.in a drying cabinet) are placed in the kneading chamber (item number279061) of the Brabender absorptometer “E” (without damping of theoutput filter of the torque sensor). In the case of granules, the sievefraction from 3.15 to 1 mm (stainless steel sieves from Retsch) is used(by gentle pressing of the granules with a plastic spatula through thesieve with a mesh size of 3.15 mm). Dibutyl phthalate is added dropwiseto the mixture at ambient temperature at a rate of 4 ml/min using the“Brabender T 90/50 Dosimat” while continuously mixing (rotational speedof the kneader blades: 125 rev/min). Incorporation is carried out withonly a low power demand and is followed using the digital display.Towards the end of the determination, the mixture becomes pasty, whichis indicated by a steep rise in the power demand. When the display shows600 digits (torque of 0.6 Nm), both the kneader and the DBP metering areswitched off via an electrical contact. The synchronous motor for thefeeding of DBP is coupled to a digital counter so that the DBPconsumption in ml can be read off.

The DBP absorption was given in the unit [g/100 g] without decimalplaces and was calculated from the following formula:

${DBP} = {\frac{C*D*100}{S} + F}$with

DBP=DBP absorption in g/100 g

C=DBP consumption in ml

D=density of DBP in g/ml (1.047 g/ml at 20° C.)

S=starting weight of silica in g

F=correction factor according to moisture content correction table ing/100 g

The DBP absorption was defined for the anhydrous dried silica or silicagel. If hydrous preciptated silicas or silica gels are used, thecorrection factor F is to be taken into consideration in the calculationof the DBP absorption. This factor can be determined from the followingcorrection table, e.g. a water content of the silica of 5.8% would meanan increase of 33 g/(100 g) for the DBP absorption. The moisture contentof the silica was determined according to the method “Determination ofthe moisture content or of the loss on drying” described subsequently.

Moisture content correction table for dibutyl phthalate absorption(anhydrous)

% Moisture .% Moisture Content Content .0 .2 .4 .6 .8 0 0 2 4 5 7 1 9 1012 13 15 2 16 18 19 20 22 3 23 24 26 27 28 4 28 29 29 30 31 5 31 32 3233 33 6 34 34 35 35 36 7 36 37 38 38 39 8 39 40 40 41 41 9 42 43 43 4444 10 45 45 46 46 47

Determination of the Moisture Content or of the Loss on Drying

The moisture content or even loss on drying (LD) of silicas weredetermined according to ISO 787 2 after drying at 105° C. for 2 hours.This loss on drying consisted predominantly of water.

10 g of the pulverulent, spherical or granular silica were weighed outexactly to 0.1 mg in a dry weighing bottle with a ground-glass lid(diameter 8 cm, height 3 cm) (starting weight S). The test specimen wasdried with the lid open at 105±2° C. for 2 h in a drying cupboard.Subsequently, the weighing bottle was closed and cooled down to ambienttemperature in a dessicator cabinet with silica gel as drying agent.

The weighing bottle was weighed accurately to 0.1 mg on a precisionbalance, in order to determine the final weight F. The moisture content(LD) is determined in % according toLD(1−F/S)*100,

where F=final weight in g and S=starting weight in g.

Determination of the Tapped Density

The tapped density was determined according to DIN EN ISO 787-11.

A defined amount of a test specimen was not sieved beforehand thenpoured into a graduated glass cylinder and subjected to a specificnumber of taps using a jolting volumeter. During the tapping, the testspecimen becomes compressed. As a result of the investigation carriedout, the tapped density was obtained.

The measurements were carried out on a jolting volumeter with a counterof STAV 2003 type from Engelsmann, Ludwigshafen.

A 250 ml glass cylinder was first tared on a precision balance.Subsequently, 200 ml of silica were poured into the tared measuringcylinder using a powder funnel so that no void spaces are formed. Thiswas achieved by tilting and rotating the cylinder about its longitudinalaxis during the pouring operation. Subsequently, the amount of testspecimen is weighed accurately to 0.01 g. The cylinder was then gentlyrapped so that the surface of the silica in the cylinder was level. Themeasuring cylinder was put into the measuring cylinder holder of thejolting volumeter and tapped 1250 times. The volume of the tapped testspecimen is read off accurately to 1 ml after a single jolting pass.

The tapped density D(t) was calculated as follows:D(t)=w*1000/V

-   -   D(t): tapped density [g/l]    -   V: volume of the silica after tapping [ml]    -   w: weight of the silica [g]

The following examples serve exclusively to more fully explain thepresent invention but do not, however, limit it in any way.

Determination of the Density of the Liquid Particular Substance for Usein Plant Protection Compositions or of the Liquid Mixture of ParticularSubstances for Use in Plant Protection Compositions

The determination was carried out using a density hydrometer accordingto DIN 12791, Part 3. The reference temperature is 20° C.

EXAMPLES

Sipemat 22 S with a micropore volume<2 nm of 0.02 ml/g and ameso/macropore volume of 3.6 nm-100 nm of 1.38 ml/g was used for thepreparation of the active substance absorbates. This corresponded to aproportion of macropore volume of 1.43%. The DBP of the Sipernat 22 Sused was 265 g/100 g.

Example 1 Preparation of an Active Substance Absorbate Suitable forDirect Use as WP or for Further Processing to Give WP or WG

Chemicals:

Sipernat 22 S 200 g Malathion (Fyfanon 96-97%, Cheminova) 756.5 g Berol916 (Akzo Nobel) 43.5 g Empikol LZ (Albright & Wilson) 43.5 g

The wetting agent Berol 916, preheated to 50° C., was dissolved in themalathion with stirring. The density of the solution at 20° C. is 1.222g/ml. The liquid solution, cooled down to ambient temperature, was fedfrom a feed vessel to a pressure-resistant static mixer into whichcompressed carbon dioxide was simultaneously metered. The conditions inthe static mixer were chosen so that carbon dioxide is present in thesupercritical condition (P=100 bar; T=32° C.). Liquid and CO₂ wereintensively mixed with one another and some part of the supercriticalgas dissolves in the liquid, producing a solution saturated with gas.

Finally, the solution saturated with gas is expanded in the spray towervia a high pressure nozzle. Dissolved carbon dioxide is present in thedroplets formed by the nozzle and escapes abruptly from these dropletsin the expansion to atmospheric pressure, further reducing the dropletsin size. Sipernat 22 S, fluidized in a stream of CO₂ gas, issimultaneously metered as carrier right into this mist of very finedroplets. Turbulent flow around the high pressure nozzle ensuredintensive contact between liquid droplets and Sipemat 22 S and theliquid was bonded to the carrier. The powder formed settled out in thespray tower and is discharged batchwise.

The active substance absorbate thus obtained, with a concentration byweight of particular substances (malathion+Berol 916) for use in plantprotection compositions before standardization of X_(before)=80% andafter standardization of X_(stand.)=76.6%, based on the total weight ofthe absorbate, had mixed into it mechanically the solid pulverulentdispersant Empikol LZ and, accordingly, a ready-for-use plant protectioncomposition formulation was prepared.

Comparative Example Preparation of an Active Substance AbsorbateAccording to a Conventional Process of the State of the Art

Chemicals:

Sipernat 22 S 31 g Malathion (Fyfanon 96-97%, Cheminova) 52.1 g Berol916 (Akzo Nobel) 3.0 g Empikol LZ (Albright & Wilson) 3.0 g

Sipemat 22 S and the dispersant Empikol LZ are placed, according to theamounts in the preceding list, in a 500 ml Quickfit glass stirringdevice with a precision bearing stirrer and briefly mixed. A solution ofmalathion and the wetting agent Berol 916, prepared according to Example1, is added thereto dropwise inside 30 minutes with stirring, andstirring is carried out for a further 5 minutes. The absorbate obtainedexhibited a of particular substances for use in plant protectioncompositions (malathion+Berol 916) of X_(before)=64%. This correspondsto a standardized content by weight of X_(stand.)=59.3%.

Increasing the amount of liquid added in the comparative example to thepercentage given in Example 1 resulted, in this conventional process, inoverloading of individual silica particles and accordingly in anagglomerated mixture which is very firmly stuck together and whichcannot be used further. In contrast to this, flowable, superficiallydry, agglomerated absorbate particles were obtained in Example 1 whichare suitable for further processing or, according to the agglomeratesize, for direct use as WP or WG.

The entire contents of German Application No. 102006002765.5 areincorporated herein by reference.

The invention claimed is:
 1. An absorbate, comprising: at least onecarrier material selected from the group consisting of a precipitatedsilica, a pyrogenic silica, a silica gel, a natural clay, a modifiednatural clay and a diatomaceous earth; and at least one particularsubstance for use in plant protection compositions or a mixture ofsubstances comprising at least one particular substance for use in plantprotection compositions; wherein the total amount of the particularsubstances for use in plant protection compositions, X_(stand.), is 70%to 99%.
 2. The absorbate according to claim 1, wherein the carriermaterial has a proportion of micropore volume, based on the total porevolume, of less than or equal to 10% by volume.
 3. The absorbateaccording to claim 1, wherein the carrier material exhibits adi-butyl-phthalate absorption of greater than or equal to 150 g/100 g.4. The absorbate according to claim 1, wherein the carrier material is aprecipitated silica, a pyrogenic silica or a silica gel.
 5. Theabsorbate according to claim 1, wherein the carrier material has atapped density of less than 200 g/l.
 6. The absorbate according to claim1, wherein the carrier material has a tapped density of less than 150g/l.
 7. The absorbate according to claim 1, wherein the carrier materialhas a tapped density of less than 100 g/l.
 8. The absorbate according toclaim 1, wherein the proportion of the particular substance for use inplant protection compositions or, in mixtures of at least two of thesesubstances, the total amount of these substances, X_(stand.), is 75 to95%.
 9. The absorbate according to claim 1, comprising at least oneparticular substance for use in plant protection composition having amelting point of less than or equal to 80° C.
 10. The absorbateaccording to claim 1, comprising at least one absorbed component that isan active substance for plant protection composition.
 11. The absorbateaccording to claim 1, comprising at least one of the absorbed componentsthat is an auxiliary for plant protection compositions.
 12. Theabsorbate according to claim 1, which is a water dispersable granule orwettable powder formulation.
 13. A process for making an absorbate ofclaim 1, comprising: providing a liquid in a feed vessel, wherein theliquid comprises at least one of (1) a liquid or molten particularsubstance for use in plant protection compositions and (2) a liquid ormolten mixture of substances comprising at least one particularsubstance for use in plant protection compositions; mixing, partlydissolving, or both mixing and partly dissolving, a gas in the liquid toform a mixture; feeding the mixture to an expansion element; conveyingthe mixture through the expansion element to expand the mixture; andadding at least one solvent pulverulent carrier material to the expandedmixture.
 14. The process as claimed in claim 13, wherein the mixing,partly dissolving or both mixing and partly dissolving is carried outunder elevated pressure.
 15. The process as claimed in claim 13, whereinthe mixing, the partly dissolving or both the mixing and partlydissolving is carried out under super critical conditions.
 16. Theprocess as claimed in claim 13, wherein the mixing, the partlydissolving, or both the mixing and the partly dissolving is carrier outwith CO₂ at a pressure of greater than 73.83 bar and a temperature ofgreater than 31.04° C.
 17. The process as claimed in claim 13, whereinthe mixing, the partly dissolving or both the mixing and the partlydissolving is carried out in at least one of a mixer and a pressurizedvessel.
 18. The process according to claim 13, wherein the carriermaterial has a proportion of micropore volume, based on the total porevolume of less than or equal to 10% by volume.
 19. The process accordingto claim 13, wherein the carrier material has a di-butyl-phthalateabsorption of ≧150 g/100 g.
 20. The process according to claim 13,wherein the carrier material is a precipitated silica, a pyrogenicsilica or a silica gel.
 21. The process according to claim 13, whereinthe carrier material has a tapped density of less than 200 g/l.
 22. Theprocess according to claim 13, wherein the carrier material has a tappeddensity of less than 150 g/l.
 23. The process according to claim 13,wherein the carrier material has a tapped density of less than 100 g/l.24. An absorbate made by the process of claim
 13. 25. A plant protectionproduct comprising the absorbate according to claim
 1. 26. The productaccording to claim 25, which is a wettable powder or a water dispersablegranule formulation.
 27. A process, comprising: applying the absorbateaccording to claim 1 onto a plant.
 28. The process as claimed in claim13, wherein the mixture is at least one of a liquid/gas solution and aliquid/gas melt.
 29. An absorbate, comprising: at least one carriermaterial selected from the group consisting of a precipitated silica, apyrogenic silica, a silica gel, a natural clay, a modified natural clayand a diatomaceous earth; and at least one plant protection substanceabsorbed by the carrier material; wherein the total amount of the plantprotection substance absorbed by the absorbate is X_(stand.) of 70-99%based on the total weight of the absorbed plant protection substance andthe carrier material; wherein: $\begin{matrix}{X_{stand} = \frac{100}{{\rho_{Fl}*\left( {\frac{100}{X_{vor}} - 1} \right)} + 1}} & {{formula}\mspace{14mu}(I)}\end{matrix}$ with X_(stand.)=amount by weight standardized with regardto a liquid density of 1.00 g/ml, in %, X_(before)=amount by weightbefore standardization, in %, ρ₁=density of the absorbed particularsubstance for use in plant protection compositions or of the mixture ofparticular substances for use in plant protection compositions, in g/ml;Wherein the amount by weight before the standardization is calculatedaccording to formula (II): $\begin{matrix}{X_{before} = {\frac{W_{1\;{{abs}.}}}{W_{{abs}.{total}}}*100\%}} & {{formula}\mspace{14mu}({II})}\end{matrix}$ with W_(1 abs.)=weight of the absorbed plant protectionsubstance, in g, W_(abs. total)=total weight of the absorbate, in g. 30.The absorbate according to claim 29, wherein X_(stand.) is 75-95%.